Phenyl sulphonyl esters of nitro alcohols



Patented Feb. 26, 1946 Philip J. Baker, Jr.,"l'erre Haute, ma, assignor to J Commercial Solvents Corporation, Terre Haute, lnd., a c rp ration of Maryland No Drawing. Application February 4, 1944,

' Serial No. 521,125

.4 Claims.

The present invention relates to new chemical compounds.

phenyl sulphonyl ester of nitro alcohols and to a process for the preparation thereof. a The new chemical compounds of my invention may be represented by the following general'structural formula:

wherein X represents a substituent selected from the group consisting of hydrogen, alkyl and acylamino, R represents a substituent of-the group consisting of hydrogen and alkyl, Ar represents a phenyl nucleus, while R represents an alkyl substituent.

As examples of compounds included by the above generic formula,- as well as diand triesters forming. the subject matter of copending divisional applications, Serial No. 604,082, and Serial No. 604,083 there may be mentioned 2-. nitroisobutyl p-toluenesulphonate, 2-nitrobutyl p-toluenesulphonate, 2-nitro-2-methyltrimethylene p-toluenesulphonate, tris- (p-toluenesulphonoxymethyl) nitromethane, z-nitroisobutyl benzenesulphonate, 2-nitro -'2 methyltrimethylene benzenesulphonate, 2-nitro-2-ethyltrimeth'ylene benzenesulphonate, tris(benzenesulphonoxymethyD-nitromethane, z-nitroisobutyl p-acetamido- More particularly, it relates to tiary amine and any unreacted alcohol which might be present. At this stage of the procedure, the ester will generally be observed to solidify. The product isthen. filtered and washed with water. In most cases the esters can be crystallized either from methanol or ethanol; Frequently benzene or similar hydrocarbons can be used for this purpose. I

The nitro alcohols utilized in preparing the new phenyl sulphonyl esters of my invention as well as diand tri-esterg forming the subject matter of copending divisional applications, Serial No. 604,082, and Serial No. 004,083 may be any of a large number of compounds such as, for example, 2-nitro-1-ethanoi, z-nitro-l-propanol, 2-nitro-2- methyl-l-propanol, 2-nitro-1-butanol, 2-nitro-2- methyl-1,3-propanediol, 2-nitro-2-ethyl-l.,3-propanediol, tris(hydroxym'ethyl) nitromethane, and

the like. i v

As examples of tertiary amines which maybe utilized in synthesizing the compounds of my invention, there may be mentioned pyridine, trimethy'lamine, tributyiamine, quirioline, and the like. Bases such as sodium carbonate and sodium hydroxide may also be employed in place of tertiary amines; however, it has been my general observation that the results obtained when usin benzenesulphonate, 2-nitro-2-methyltrimethylene p-acetamidobenzenesulphonate, tris(p-acetami-- dobenzenesulph'onoxymethyl)nitromethane, the like.

In accordance with my invention, compounds of the above type are prepared by first mixing a nitro alcohol with a phenyl sulphonyl halide and thereafter slowly adding to this mixture a suitable base, such as, for example, a tertiary amine. The nitro alcohol and phenyl sulphonylhalide are preferably reacted with one another in approximately equivalent quantities while the tertiary amine is generally preferably employed in a quantity slightly in excess of the equivalent amount. The initial reaction is rather vigorous and precautions should therefore be taken-in orw der to avoid decomposition of the reactants. After and - the initial stage of the reaction has been completed, however, the reaction mixture is preferably heated to a temperature of between about and C. so that the reaction is driven as nearly to completion as possible. The resultant mixture is then cooled. and water is added in order to remove the hydrogen halide of the tersuch bases are less satisfactory. Solvents, such as benzene, chloroform, and xylene, may be employed. However, it has usually been foundthat the yieldof the desired phenyl suiphonyl ester is lowerwh'en a solvent is utilized. 7

My invention may be further illustrated by the example which follows. Since the reaction involved is ve y general in character, it is considcred necessary to set forth only a singleexample of the procedure employed to! preparing thephenyl sulphonyl esters of my invention.

Exun'u:

A consisting of 8 parts of 2- nitro-2- methyl -l-propanol and 9,5 parts of p-toluenesulphonyl chloride was placed in a suitable reaction vessel, after which was slowly added thereto, with agitation, 5 parts of pyridine. When all of the pyridine had been added, the reaction mixapproximately 1 hour. and'thereaiter cooled to ture was placed on a steam bath for a period of room temperature. Twenty parts of water was next added. with stirring. As a result, the crude 2-nitroisobutyl p-toluenesulphonate precipitated. The precipitate was then altered and washed with two 20-part portions of water. This washed material was then The crystalline fl-nitroisobutyl p-toluenesulphofrom methanol.

V 'iris (benzenesulphonoxyamounted to a yield of 76.7%. a 7

Analysis: Calculated .i'or per cent N, 5.13; per

cent 5, 11.72. Found: Per cent N, 5.38; per cent y In the table which follows, there appears a list of typical compounds prepared in accordance with the procedure outlined above.

Table I Compound 4 E "Percent N z-nittobutyl p-tolueumllphom" a 2-nitro- 2 -methyltrimethylene p-toluencsulphonaw 2-nitro-Z-ethyltrimcthylcne pl-oluencsuiplmuale. 'lris (p-tolucnesulphonnxymethyl) nitmmethane 2-niti'oisobutyl benzenesulphnnate V 56 2-nitr0-2-mcthyltrimcthylcne bvnzenesuiphonatl 114 241itro-Z-ethyltrimethylene bcuzcncsulphonate 69-69. 5

a as

a. as

sec

methyl) nitrometlmnev e 2-nitroisobutyl p-acetamidw benzenesulphonate 2-nitro-2-methyltrimethy'ieue p-ucetamidobenzenesulphonate. 198 r 7.93

Galc'd. I

Per-

I aaaaaee nate thus obtained melted at IT-'13 C. and

Although the above physical properties may be helpful in identifying these compounds, it is to be understood that I do not desire to limit myself to products having the exact physical constants described above, since the data were obtained from a single preparation of the various com- The phenyl sulphonyl esters of my invention are useful for numerous purposes, particularly as plasticizers for synthetic ruber and similar type Polymers. Other uses of these products will readily occur to those skilled in the art.

My invention now having been described, what "lclaimis:

1.- Phenyl sulphonyl esters of nitro alcohols havingthe formula;

No,: a- -CH,O-s0,1u-x

l wherein Xfrpresents a substituent selected from the group consisting of hydrogen, alkyl and 1103;]- amino, R. represents a substituent of the group consisting ot'hydrogen and alkyl, Ar represents a phenyl nucleus, while R represents an alkyl substituent.

2. 2-nitrobutyl p-toiuenesulphonate.

3. 2-nitroisobutyl benze'nesulphonate. 4. 2-nitroisobutyl p-toluenesulphonate.

rmmr J. BAKER, JR. 

